Cyanoalkylamino-phenylcarbamates

ABSTRACT

AMINOPHENYLCARBAMAATES, THE AMINO GROUP OF WHICH IS SUBSTITUTED BY AT LEAST ONE LOWER ALKENKYL RADICAL SUBSTITUTED BY 1 OR 2 HALOGEN ATOMS OR BY AT LEAST ONE LOWER ALLKL RADICAL SUBSTITUTED BY A LOWER ALKOXY, ALKYLMERCAPTO OR NITRILE GROUP, ARE EFFECTIVE PESTICIDES FOR CONTROLLING NEMATODES, INSECTS AND REPRESENTATIVES OF THE ORDER ACARINA. THEY MAY BE USED AS PESTICIDAL PREPARATIONS.

States Patent 01 :"fice Patented June 25, 1974 3,819,678CYANOALKYLAMINGPHENYLCARBAMATES Erwin Nikles, Liestal, Switzerland,assignor to Ciba- Geigy Corporation, Ardsley, N.Y. N'-Drawing.Continuation-impart of abandoned applica- .tion, Sen No.;30,9 40,,Apr.22, 1970. This application D 8 1971, Ser. No, "206,163

,f a iplicatioi Switzerland, Apr. 26, 1969, V H 6,365/69/ i IntJ CL'C07c121/78 Cl. 260'-'-'-'46'5 Y I riori U 55." Claims hlisrnh cr on" THEDISCLOSURE Aminophenylcarbamates, the amino group of which issubstituted by at least one lower alkenyl radical substituted by 1 or 2halogen atoms or by at least one lower alkyl radical substituted by alower alkoxy, alkylmercapto or nitrile group, are, effective pesticidesfor controlling nematodes, insects and representatives of the orderAcarina. They may be used as pesticidal preparations.

- (:RossREFERE cE TO .RELATED -,-APPLICATIONS The instan't applicatidnis a continuation-in-part of application Ser ."No.fl30,940, filed Apr.22, 1970, now abandoned.

V it DISCL This invention relates to novel carbamates and to pesticidalpreparationscontaining them.

The present invention provides compounds of the general formula in whichR representsa Ci C -alkyl, C -C -alkenyl or C C -alkinyl or has theisame meaning as R R represents a C -C -alkenyl radical substituted by 1or 2 halogeii atoms or a C' 'C -alkyl radical substituted by a C ec-alkoxy,.Q C alkylmercapto or nitrile group, R reppesen ts a hydrogenatom or amethyl radical and R ang kg whiqh may be :the.s anie :ordifferent, each represents a hydrogen atom or a C C -alkyl radical, ifdesired, together with one or more of the following additives: solvents,diluents, dispersing agents, Wetting agents, emulsifiers, thickeners asWell as further known pesticides.

Preferably, R and R which may be the same or different, each representsa hydrogen atom or an alkyl radical having up to 4 carbon atoms.

The new active carbamateson which the pesticidal preparations of thepresent invention are based can be obtained according to the methodswhich are customary for the manufacture of this class of substances, forexample, by reaction of appropriate phenols, including nitrophenols,with alkali isocyanates or dialkylcarbamic acid chlorides, and, in thecase of the nitrophenols, reducing the nitro group to the amino andintroducing the radicals R and R The carbamates of formula (I) can alsobe obtained by reaction of appropriately substituted aminophenylchlorocarbonates or bis-[aminophenyl]-carbonates of the formula j (orbis-[nitrophenyl1-carbonates with reduction of the N0 group) withappropriate dialkylamines or alkylamines CH -NHR If a free NH group ispresent in the phenyl nucleus, its H atoms can be singly or doublysubstituted in a known manner, for example with an appropriatelyesteri-' fied p-toluenesulphonic acid or methanesulphonic acid, or withan alkyl halide or an alkenyl halide having, at most, 2 halogen atoms,preferably in the presence of an acidbinding agent. Before forming thecarbamate grouping, the phenols on which the compounds are based canalso be nitrated or nitrosylated and subsequently converted intomono-N-substituted aminophenols by reductive alkylation with anappropriate ketone or aldehyde in the presence of hydrogen and asuitable catalyst for example, palladium/charcoal, under pressure. It isalso possible to apply this mono-N-substitution directly toaminophenols; The further replacement of the second H atom of the grouptakes place as mentioned initially.

The active ingredients can be present not only as the free base but alsoin the form of their salts. Inorganic and organic acids can be used forthe formation of the salt, for example, sulphuric acid, hydrochloricacid, hydrobromic acid, phosphoric acid, sulphamic acid, citric acid,glycollic acid, ethionic acid, methanesulphonic acid, toluene-sulphonicacid, p-aminobenzoic acid, maleic acid and numerous others. Acid salts,for example, the acid sulphate, are distinguished by their especiallyfavourable stability.

The compounds of formula (I) show a broad biocidal action and can beemployed for combatting very diverse animal pests. Amongst the animalpests, there should be mentioned nematodes, insects and representativesof the order Acarina, for example, mites and ticks, as well as all theirstages of development, such as eggs, lanvae and chrysales or pupae.

The compounds of formula (I) can, for example, be used against allharmful insects, for example, against leafhopper in rice cultures,against aphids, such as the green peach aphid (Myzus p'ersicae). and thebean aphid (Doralis fabae); shield lice such as Aspidiotus heder ae,Lecanium hesperz'dium and Pseudococcus maritim-us; Thysanoptera such asHerci nothrips femoralis, and bugs such as the beet bug (Piesmaq'udrata) or the bed bug (Cimex lectularius), butterfly caterpillars,such as Plutella maculipennis and Lymantria dispar; beetles such as thegranary weevil (Calandra granaria) or the Colorado beetle (Leptinotarsadecemlineata), but also varieties which live in soil, such as wireworms(Agriotes sp.) or cockchafer grubs (Melolontha melolontha); Orthopterasuch as the German cockroach (Blattella germanica) or the house cricket(Gryllus domestz'cus); termites, such as Reticulitermes; Hymenoptera,such as ants; Diptera such as the vinegar fly (Drosophila melanogaster),the Mediterranean fruit fly (Ceratitis capitata) and the house fly(Musca domestica) as well as gnats (for example Aedes aegypti andAnopheles stephensi).

In respect of contact action, the compounds of the present invention aregreatly superior to the known active substanceN-methyl-ot-naphthylcarbamate.

The compounds of the formula (I) are also especially effective incombatting representatives of the order Acarina, for example, Eulaelaps,Echniolaelaps, Laelaps, Haemogamasus, Dermanyssus, Ornithenyssus,Allodermanyssus, especially Allodermanyssus sanguineus, Pneumonyssus,Amblyomma, Aponomma, Boophilus, Dermacentor, Haemophysalis, Hyalomma,Ixodes, Margaropus, Rhipicephalus, Ornithodorus; Otobius, Cheyletidae,for example, Cheyletus, Psorergates, Demodicidae, Trombiculidae, forexample, Trombicula, Eutrombicula, Schongastia, Acomataeurus,Neoschongastia, Euschtingastia, Sarcoptiformes, for 'example, Notoedres,Sarcoptes, Knemidokoptes, Psoroptidae, for example, Psoroptes,Chorioptes, Octodectes or Tetranychidae, for example, Tetranychustelarius, Tetranychus ureticae and the like.

In general, the active substances of formula (I), by themselves or inagents, show a high contact poison and bait poison action againstinsects, nematodes and pests of the order Acarina.

Their broad action spectrum makes them, above all, suitable forcombatting pests in the following cultures: cotton, rice, maize, kernelfruit and stone fruit, and lucerne. They act against the Lepidoptera,Coleoptera, Rhynchota and Hymenoptera which become particularlydangerous to these cultures. Attention should be drawn especially to theexcellent action against larvae of noctuids, such as Prodenia litura andProdenia ornithogalli, and weevils such as Anthonomus grandis, whichoccur on cotton and other cultures.

When used in plant protection in a concentration which does not permitany phytotoxic phenomena to arise, the active substances of formula (I)also show a good action against harmful micro-organisms, for exampleagainst fungi, for example, Alternaria s lani, Phytophthora infestansand Septoria apii, as Well as against microorganisms, for example,varieties of Aspergillus, and also molluscs, especially gastropodes,which are known as schistosome carriers.

The advantageous toxicities towards warmblooded animals of the compoundsaccording to the invention should be highlighted.

Preferred are the compounds of the general formula CHaNHC wherein R,represents a C -C -alkyl radical or has the same, meaning as R' R'represents a C C -alkenyl radical substituted by a halogen atom or a C-C -alkyl radical substituted by a C -C -alkoxy or nitrile group and Rrepresents a hydrogen atom or a methyl, ethyl or isopropyl radical.

Another group of preferred compounds is that of the general formulaCHaNHCO? CHaNHC O 0 R4 R: (IV) wherein R' represents a C -C -alkylradical or has the same, meaning as -R R' represents a C -C -alkenylradical substituted by a halogen atom or a C -C -a1kyl radicalsubstituted by a C -C -alkoxy or nitrile group and R'4 and R eachrepresents a hydrogen atom or a methyl, ethyl or isopropyl radical.

Special interest attaches to those compounds of the formula as the freebase or in the form of its salts, in which R" represents a C C -alkylradical and R" represents a C -C -alkyl radical substituted by a nitrilegroup.

Another group of outstandingly active substances is that having thegeneral formula RH! RIII, I in which R"' represents a C -C -alkylradical or has the same meaning as R" R"' represents a C C -alkenylradical substituted by l halogen, especially a chlorine atom and RC; andR' which may be the same or different, each represents a hydrogen atomor a methyl, ethyl or isopropyl radical.

Another group of interesting active substances is that having thegeneral formula N R R X rm in which R represents a C -C -a1ky1 radicalor has the same meaning as R R represents a C -C -alkyl radi calsubstituted by a nitrile group and R'.; and R' which (61 2-(Cyanomethyl-isopropyl-amino) -phenyl-N- methylcarbamate, (62) 2-(Allyl-B-cyanethybamino -phenyl-N-methylcarbamate, (63)2-(B-Cyanethyl-propargyl-amino)-phenyl-N- methylcarbamate, (64) 2-(B-Methoxyisopropyl-methylamino) -phenyl-N- methylcarbamate, (65 4- [Bis(fl-cyanethyl) -amino] -3-isopropyl-phenyl-N- methylcarbamate, oil, (66)4-(B-Cyanethyl-methyl-amino)-3-isopropyl-phenyl- N-methylcarbamate, oil,(67) 4(,S-Cyanethyl-ethyl-amino)-3-isopropyl-phenyl-N- methylcarbamate,oil, (68) 4-(' -Chlorallyl-ethyl-amino)-3-methyl-phenyl-N-methylcarbamate, oil, (69) 4-(-Chlorallyl-ethyl-amino)-3-isopropyl-phenyl- N-methylcarbamate, oil,(70) 4-(Cyanomethyl-methyl-amino)-3-methyl-phenyl- N-methylcarbamate,oil, (71 4- (Cyanomethyl-methyl-amino) -3-1sopropy1-phenyl-N-methylcarbamate, oil, (72)4-(Cyanomethyl-methyl-amino)-3,5-d1methylphenyl-N-methylcar-bamate, oil,(73 4- (B-Chlorallybmethyl-amino -3,5-d1methyl-phenyl-N-methylcarbamate, melting point 80 C., (74)4-('y-Chlorallyl-methyl-amino)-3,5-dimethyl-phenyl- N-methylcarbamate,oil, (75) 4- [BisOy-chlorallyl) -amino] -3 -sec.butyl-phenyl-N-methylcarbamate, oil, (76) 3-(Cyanomethyl-isopropyl-amino)-phenyl-N-methylcarbamate, dark oil, (77) 3- (Cyanomethyl-methyl-amino-phenyl-N-methylcarbamate, viscous oil, (78 3-(Cyanomethyl-methyl-amino) -4-methyl-phenyl- N-methylcarbamate, oil,(79) 3-(# Cyanethyl-methyl-amino)-4-methyl-phenyl N-methylcarbamate,oil, (80) 3-[Bis(B-cyanethyl)-amino]-phenyl-N-methylcarbamate, meltingpoint 150-153 C., (8 1 3- (p-cyanethyl-ethyl-amino)-phenyl-N-methylcarbamate, oil, (82)3-(p-Chlorallyl-isopropyl-amino)-phenyl-N-methylcarbamate, melting point88-92 C., (83)3-(Cyanomethyl-isopropyl-amino)-4-methylphenyl-N-methylcarbamate, oil,(84) 3-(Cyanomethyl-ethyl-amino)-4-methyl-phenyl-N- methylcarbamate,yellow oil, (85 3- (fl-Cyanethyl-ethyl-amino) -4-methyl-phenyl-N-methylcarbamate, yellow oil, (86) 3-('-Chlorallyl-isopropyl-amino)-4-methyl-phenyl- N-methylcarbamate, yellowviscous oil, (87) 3-(y-Chlorallyl-ethyl-amino)-4-methyl-phenyl-N-methylcarbamate, viscous oil,

(88) 3- (-y-Chlora1lyl-methyl-amino)-4-methyl-phenyl- (98) 4- [Bis(fi-cyanethyl) -amino]-2,3-dimethyl-phenyl- N-methylcarbamate, oil,

(99) 4- [BisOy-chlorallyl) -amino]-3-(u-methylbuty1)-phenyl-N-methylcarbamate, viscous oil,

( 100) 4- [Bis('y-chlorallyl)-amino] -3-(u-ethylpropyl)phenyl-N-methylcarbamate, viscous oil,

( 101 2- Cyanomethyl-ethyl-amino) -phenyl-N-methy1- carbamate, meltingpoint 86 C.,

( 102) 2- (Cyanomethyl-n-propyl-amino) -phenyl-N- methylcarbamate,melting point 5565 C.,

(103) 2-(Cyanomethyl-n-butyl-amino)-phenyl-N- methylcarbamate, meltingpoint 72-765 C.,

( 104) 2-(Cyanomethyl-propargyl-amino) -phenyl-N- methylcarbamate,

( 105 3- Cyanomethyl-n-butyl-amino -phenyl-N- methylcarbamate, meltingpoint 107l09.5 C.,

(106) 3-[Bis(5-ch1orallyl) -amino]-4-methyl-phenyl- N-methylcarbamate,oil,

(107) 2- (B-Chlorallyl-ethyl-amino -4-methylphenyl- N-methylcarbamate,red oil,

( 108) 2- fi-Chlorallyl-methyl-amino) -4-methylphenyl-N-methylcarbamate, melting point 51.5-60 C.,

( 109) 2-('y-Chlorallyl-methyl-amino)-4-methylphenyl- N-methylcarbamate,oil,

(1 10)2-(,B-Chlorallyl-isopropyl-amino)-4-methylphenyl-N,N-dimethylcarbamate,oil,

(11 l) 4- [Bis ('y-Chlorallyl)-amino]-3,5-dimethylphenyl-N,N-dimethylcarbamate, oil,

( 112) 4- ('y-Chlorallyl-methyl-amino-3,5-dimethylphenyl-N,N-dimethylcarbamate, oil.

The new agents can be employed in the most diverse manner and in variousforms, for example in the form of sprays, dusting powders, fly dishes orstrips which are impregnated with a solution of the active substances.

In order to manufacture directly sprayable solutions of the compounds ofgeneral formula (I), it is for example possible to use mineral oilfractions of high to medium boiling range, such as diesel oil orkerosene, coal tar oil and oils of vegetable or animal origin, as wellas hydrocarbons, such as alkylated naphthalenes ortetrahydronaphthalene, optionally with the use of xylene mixtures,cyclohexanols, ketones and also chlorinated hydrocarbons such astrichlorethane and tetrachlorethane, trichlorethylene ortrichlorebenzenes and tetrachlorobenzenes. Advantageously, organicsolvents of boiling point above C. are used.

Aqueous application forms are particularly appropriately prepared fromemulsion concentrates, pastes or wettable spraying powders by addingwater. Possible emulsifiers or dispersing agents are non-ionic products,for example condensation products of aliphatic alcohols, amines orcarboxylic acids having a long-chain hydrocarbon radical of about 10 to20 carbon atoms with ethylene oxide, such as the condensation product ofoctadecyl alcohol and 25 to 30 mols of ethylene oxide, or that oftechnical oleylamine and 15 mols of ethylene oxide or that ofdodecylmercaptan and 12 mols of ethylene oxide. Amongst the anionicemulsifiers which can be employed, there may be mentioned: the sodiumsalt of dodecyl alcohol sulphuric acid ester, the sodium salt ofdodecylbenzenesulphonic acid, the potassium or triethanolamine salt ofoleic acid or of abietic acid or of mixtures of these acids, or thesodium salt of a petroleum-sulphonic acid. Possible cationic dispersingagents are quaternary ammonium compounds, such as cetylpyridiniumbromide, or dihydroxyethylbenzyldodecylammonium chloride.

In order to manufacture dusting agents and scattering agents, talc,kaolin, bentonite, calcium carbonate or calcium phosphate, but alsocharcoal, cork powder, wood flour and other materials of vegetableorigin, can be employed as solid carriers. Preparations in a granularform are also very suitable.

Such granules can be manufactured very simply by dissolving an activesubstance of formula (I) in an organic solvent, applying the solutionthus obtained to a granular mineral, for example attapulgite, SiOgranicalcium, bentonite and the like and then again evaporating theorganic solvent.

It is also possible to use polymer granules. Theycan be manufactured bymixing the active substances of formula (I) with polymerisable compounds(urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde orothers), after which a mild polymerisation is carried out, which leavesthe active substances unaffected, and the granulation is effected whilstgel formation is still taking place. A more advantageous method is toimpregnate finished, porous polymer granules (urea/ formaldehyde,polyacrylonitrile, polyesters or others) having a definite surface areaand an advantageous predeterminable adsorption/ desorption ratio withthe active substances, for example in the form of their solutions (in alow-boiling solvent) and to remove the solvent.

Such polymer granules can, in the form of microgranules with bulkdensities of preferably 300 g./litre to 600 g./litre, also be appliedwith the aid of dusting devices. The dusting can be carried-out overlarge areas of crops with the aid of aircraft.

Granules are also obtainable by compacting the carrier material with theactive substances and additives and subsequent comminution. The varioususe forms can, in the customary manner, be provided with additions ofsubstances which improve the distribution, the adhesion, the rainresistance or the penetrating power; as such substances there may bementioned: fatty acids, resin, glue, casein or alginates.

The concentration of the agents employed can vary within wide limitsdepending on the nature of the use. It is generally 0.01 percent byweight to 20 percent by weight for more dilute agents, Whilst moreconcentrated agents contain 20 percent by weight to 98 percent by weightof active substance. Very highly concentrated preparations are, say,used in the so-called ULV technique (ultra-low volume) with minimalamounts of additives. The ULV technique is used with very finelyatomising spraying devices, preferably with the aid of aircraft.

The action of the carbamates according to the invention can ,be furtherincreased by synergistic agents. Suitable materials for this purposeare, for example, Sesamine, Sesamex, piperonylcyclonene, piperonylbutoxide, piperonal-bis[2-(2 butoxyethoxy) ethyl] acetate, sulphoxides,propyl isome, N-(2-ethylhexyl)-5-norbornene-2,3-dicarboxyamide,octachlorodipropyl ether, 2-nitrophenylpr'opargyl-ether and2,4,S-trichlorophenyl-propargyl-ether.

The active substances according to the invention can be employed inagents by themselves or together with customary pesticides, especiallyinsecticides, acaricides, nematocides, bactericides and fungicides.

The following list gives some examples relating to the combination ofsuitable insecticides, acaricides and nematocides.

PHOSPHORIC ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride(TEPP) 0,0,0,0-TetrapropyldithiopywphosphateDimethyl(2,2,2-trichloro-1-hydroxyethyl)phosphonate Trichrorfon) 11,2-Dibromo-2,2-dichlorethyldimethylphosphate (Naled)2,2-Dichlorovinyldirnethylphosphate (Dichlorfos)Z-Methoxycarbamyl-1-methylvinyldimethylphosphate (Mevinphos) Dimethyl-1-methyl-2- methylc arbamoyl) vinylphosphate cis (Monocrotophos)3-(Dimethoxyphosphinyloxy)-N-methyl-N-methoxy-ciscrotonarnide3-(Dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (Dicrotophos)2-Chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate(Phosphamidon) 0,0-Diethyl-O(or S) -2- (ethylthio)-ethylthioph0sphateDemeton) S-Ethylthioethyl-0,0-dimethyl-dithiophosphate (Thiometon)0,0-Diethyl-S-ethylmercaptomethyldithiophosphate (Phorate)0,0-Diethyl-S-2- (ethylthio ethyl] dithiophosphate (Disulfoton)O,O-Dimethyl-S-2 -(ethylsulphinyl)ethylthiophosphate (Oxydemetonmethyl)0,0-Dimet hyl-S( 1,2-dicarbethoxyethyl) dithiophosphate (Malathion)0,0,0, O-Tetraethyl-S,S'-methylene-bis- [dithiophosphate] (Ethion)O-Ethyl-S,S-dipropyldithiophosphate 0,0-Dimethyl-S- (N-methyl-N-formylcarbamoylmethyl) dithiophosphate (Formotion)0,0-Dimethyl-S-(N-rnethylcarbarnoylmethyl)dithiophosphate (Dimethat)0,0-Dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (Ethoat-Methy'l)0,0-Diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate (P'rothoat)S-N- 1-Cyano-1-methylethyl) carbamoylmethyldiethylthiolphosphate(Cyanthoat) S-(2-Acetamioethyl)-0,0-dimethyldithiophosphateHexamethylphosphoric acid triamide (HEMPA)-0,0-DimethyPO-p-nitrophenylthiophosphate (Parathion- Methyl)0,0-Diethyl-O-p-nitrophenylthiophosphate- (Parathion)O-Ethyl-O-p-nitrophenylthiophosphonate (EPN)0,0-Dimethyl-O-(4-nitro-m-tolyl)thiophosphate (Fenitrothion)0,0-Dimethyl-O(2-chloro-4-nitrophenyl)thiophosphate (Dicapthon)0,0-Dimethyl-O-p-cyanophenylthiophosphate (Cyanox)O-Ethyl-O-p-cyanophenylphenylthiophosphonateO,'O-Diethyl-O-2,4-dichlorophenylthiophosphate (Dichrofenthion)O-2,4-Dichlorophenyl-O-methylisopropylamidothiophosphate0,0-Dimethyl-O-2,4,5-trichlorophenylthiophosphate (Ronnel)O-Ethyl-O-Z,4,5-trichlorophenylethylthiophosphonate (Trichloronat)0,0-Dimethyl-0-2,5-dichloro-4-bromophenylthiophosphate (Bromophos)0,0-Diethyl-O-2,S-dichloro-4-brornophenylthiophosphate Bromophos-Ethyl)'O,O-Dimethyl O (2,5 -dichloro-4-iodophenyl) -thiophosphate(Iodofenphos) 4-tert.Butyl-2-chlorophenyl-N-methyl-O-methylamindophosphate (Crufomat)Dimethyl-p-(methylthio)phenylphosphate 0,0-Dirnethyl-O- 3-methyl-4-methylmercapltophenyl) thiophosphate (Fenthion)Isopropylamino-O-ethyl-O- (4-Methylmercapto-3 -methylphenyl)phosphate0,0-Diethyl-O-pmethylsulphinyl) phenyl] -thiophosphate (Fensulfothion)0,0-Dimethyl-O-p-sulphamidophenylthiophosphate 0- [p-(Dirnethylsulphamido phenyl] ogO dimethylthiophosphate (Famphur)0,0,0'O'-Tetramethyl-0,0'-thiodi-p-phenylenethiophosphate0-(p-Chlorophenylazophenyl)-0,0-dimethylthiophosphate (Azothoat)O-Ethyl-S-phenyl-ethyldithiophosphonateO-Ethyl-S-4-chlorophenyl-ethyldithiophosphonateO-Isobutyl-S-p-chlorophenyl-ethyldithiophosphonate0,0-Dimethyl-S-p-chlorophenylthiophosphonate0,0-Dimethyl-S-(p-chlorophenylthiomethyl)-dithiophosphate 0,0-Diethyl-pchlorophenylmercaptomethyl-dithiophosphate (Carbophenothion) 1 5FORMULATION EXAMPLES Dusting agents Equal parts of an active substanceaccording to the invention and of precipitated silica are finely ground,Dusting agents preferably containing l6% of active substance can bemanufactured therefrom by mixing with kaolin or talc..

Spraying powders (wettable powder) In order to manufacture a sprayingpowder which is soluble in water, the following components are mixed andfinely ground:

50 parts of active substance according to the present invention,

20 parts of Hisil (highly adsorbent silica),

25 parts of bolus alba (kaolin),

1.5 parts of sodium 1-benzyl-2-stearyl-benzimidazole- 6,3-disulphonate,and

3.5 parts of a reaction product of p-tert.octylphenol and ethyleneoxide.

Emulsion concentrates (a) 40 parts of an active substance of formula (I)are mixed with 10 parts of a mixture of an anionic surfaceactivecompound, preferably the calcium or magnesium salt ofmonolauryl-benzene-monosulphonic acid, and a non-ionic surface-activecompound, preferably a polyethylene glycol ether ofmonosorbitol-laurate, and the whole is dissolved in a little xylene. Themixture is made up to 100 ccs. with xylene and a clear solution is thusobtained, which can be used as a spraying agent concentrate and whichyields a stable emulsion on pouring into water.

(b) Easily soluble active substances can also be formulated as anemulsion concentrate according to the following instruction:

parts of active substance,

70 parts of xylene, and

10 parts of a mixture of a reaction product of an alkylphenol withethylene oxide and calcium dodecylbenzenesulphonate are mixed. Ondilution with water to the desired concentration, a sprayable emulsionresults.

Granules (a) 7.5 g. of one of the active substances of formula (I) aredissolved in 100 ccs. of acetone and the acetone solution thus obtainedis added to 92 g. of granular attapulgite (mesh width: 24/48meshes/inch). The whole is well mixed and the solvent is stripped off ina rotary evaporator. Granules containing 7.5% of active substance areobtained.

(b) To manufacture 10% strength polymer granules, 1050 to 1100 g. oftechnical quality active substance of formula (I) are dissolved in 2litres of trichlorethylene and sprayed in a fluidised bed granulator,under 1.5 atmospheres gauge spraying pressure, onto 9230 g. of initiallyintroduced porous urea/HCHO granules. The solvent can be removed againby heating the fiuidising air to about 50 C.

(c) To manufacture granules containing 7.5% of the additive, 770 g. of asolid technical grade active substance of formula (I), 500 g. of BaSO1000 g. of urea and 7730 g. of powdery porous polyacrylonitrile arepressed on a roll mill and subsequently broken up to the desiredparticle size.

In the examples which follow, parts by weight are described as parts.

EXAMPLE 1 2- fi-Methoxyethyl-methyl-amino) -phenol 138 parts offi-methoxyethyl-p-toluenesulphonate are added dropwise at 60 C. to 62parts of Z-methylaminophenol, 83 parts of potassium iodide, 47.5 parts"of pyridine and 420 parts by volume of dimethylformamide. The mixture iskept for 14 hours at 40 C., cooled and poured into 2200 parts of icewater containing 100 parts of calcined sodium carbonate. The product isisolated by extraction with ether and distilled in a high vacuum. Meltmgpoint C./0.02 mm. Hg.

2- (B-Methoxyethyl-methyl-amino -phenyl-N-carbamate EXAMPLE 22-Methyl-fl-methylmercaptoethyl-amino -phenol 74 parts of3-chlorethyl-methyl-sulphide are added dropwise at 60 'C., in a nitrogenatmosphere, to a mixture of 62 parts of 2-methylaminophenol, 17 parts ofpotassium iodide, 53 parts of pyridine and parts by volume ofdimethylformamide. Themixture is stirred for 24 hours at the abovetemperature and is then cooled to room temperature, mixed with 300 partsby volume of acetone and filtered after 10. minutes. The filtrate isevaporated in vacuo and the residue is dissolved in 1000 parts by volumeof toluene, .washed with water, dried and again evaporated. Oily2-(methyl-fi-methylmercaptoethyl-amino)-phenol is obtained as theresidue.

2- (Methylfl-methylmercaptoethyl-amino)-phenyl-N- methylcarbamate 2(Methyl fl-methylmercaptoethyl-amino)-phenol is reacted withmethylisocyanate in the presence of diethylenediamine analogously to theprocess described in Examples 1-3. 2 (Methyl 3methylmercaptoethylamino)-phenyl-N-methylcarbamate is obtained as aviscous oil [Compound No. 53].

NMR-spectrum: 6 (CDCI 2.08 (s, 3H, S-CE 2.78 (s, N-Cg 2.87 (d, J=5 Hz,NH'CEg), 2.4-3.4 (m, N-CE -CE -S-CHQ, approx. 5.2 (b, 1H, NgCH 6.8-7.3(m, 4H, aromat. H).

EXAMPLE 3 2 fl-Cyanethyl-methyl-amino) -phenol 5 parts of copper-Ichloride followed, at 75 C., by 63.5 parts of acrylonitrile in portions,were added to a solution of 123 parts of Z-methylaminophenol in 400parts by volume of glacial acetic acid. The mixture is stirred for 14hours at 75 C. and is then poured onto a mixture of 700 parts ofcalcined sodium carbonate and 4000 parts of ice and water. The oilyproduct is isolated by extraction with toluene.

2- (p-Cyanethyl-methyL amino) -phenyl-'N-methylcarbamate 1 46 parts ofmethylisocyanate are added dropwise at 32-37 C., with mild cooling, to asolution of 87 parts of crude 2-(fl-cyanethyl methyl-amino)-phenol and0.5 part of triethylenediamine in 300 parts by volume of carbontetrachloride. The solution is kept at 40 C. for 14 hours andevaporated. The residue is treated with a mixture of 70 parts by volumeof concentrated hydrochloric acid and parts of water andthe mixture isextracted with toluene. The aqueous solution containing hydrochloricacid is neutralised with sodium hydroxide solution. The product isisolated by extraction with ethylgacetate. It crystallises on standing.Melting point 52-55 C. [Compound No. 57].

Hydrochl de.

3 (fl-Chlorallyl-isopropyl'arnino)-phenyl-N-methyl carbamate By.reaction of 90 parts of 3-(2-chlorallylisopropylainino)pheno1 with 34parts ot methylisocyanate in ethyl acetate in the presence of 0.5 partof triethylenediamine at 451C. for 14 hours. l VI elting point 88-92 C.(after 'e v t r ir ati n fr m YQ PP Xan .[Qo

EXAMPIJE I 3-(Cyanomethyl isopropylamine)phenol 167 parts ofiodacetonitrile are added dropwise at 60 C., in a nitrogen atmosphere,to asolution of 122 parts of 3-isopropylaminophenol in"'107 parts of2,6-lutidine and 250 parts by volume ofdirnethylformamide. The mixtureis stirred for l t-hours at 60 C., evaporated in a high vacuum, and theresidue:dilu ted with 1000 parts by volume of ether. Theether solutionis washed with water, dried over anhydrous sodium sulphate, filtered andevaporated. 135 parts of 3 (cyanomethyl isopropylamino) phenolareobtained as'a'dark oil.

. 3-K cyanomethyl isopiopylamino )phenyLN-methyll W schem3-'(Cyanomethyl-isopropylamino)phenyl N methylcarbamate is'o'btained asdescribed-in the preceding examplesfrom"3*(cyanomethyl-isopropylamino)-phenol by reaction withmethylisocy-anate in ethyl acetate at 40 C. It is obtained as a dark oil[Compound No. 76]

" "EXAMPLE 6 4-[Bis('y-chlorallyl )iamino1-3-methyl-phenol 123 parts of4-amino-3-ii1ethyl-phenol are suspended in 500 parts ofwaterinanitrogen, atmosphere and 133 parts or calcined sodium carbonateand 8.5 parts of potassium iodideam addedif278j parts of a technicalmixture of cis and trans-1,3 -dichloropropeiiefare added dropwise tothis suspension at 50?" C wl' 1ilst,stirring. The mixture is stirredfor24 hours at v50";(3. The oily product is dried, filtered andeyaporatedl'gO ly 4-[bis0y-chlorally) amino] 3-methyl-phenol is obtainedas th' residue.

4-[Bis('y clil6rally)'amino] 3*methyl-phenyl-N-methylcarbamate 1630parts of 4-[bis(l\ichlorallyl) amino] 3 methylphenol and parts oftriethylenediamine are dissolved in 2000 parts by volume of carbontetrachloride and treated drop'wise with a totaLof 3 7.6;-parts ofmethylisocyanate. The solution is kept for'*-; 1"4 hours at 40 C.,initially by external cooling and subsequently by application of heat.4-[Bis('y-chlorallyl)amiiioj33-methyl-phenyl N methylcarbama-te, whichgradually crystallises, is obtained by evaporation invacuo. .Afteronecrystallisation from toluiene-hexane', the

product melts 1at 72-78? C. [Compound ride is obtained by dissolving theproduct in hydrochloric acididiluted to half strength. 1

Acid sulphate- 3.3 parts ;of-

ts l-chlorallyl] svmethylphenyl-N-methylcarbarnate.are introduced into amixtureof 2 parts -of-vconcentrated sulphuric acid and 8. 4.

JAB iiidh sdiiiddhldi the hydrochloapproximately 6 leaves aredipped-into aqueous disperparts of water. On gentle warming, an of'the'acid sulphate is obtainedz:

EXAMPLE 7"" I 4-[Bis(fl-methoxyethyl)amino]-3-methyl-phenol A stirredmixture of 62 .parts of 4-amino-3 methylphenol '83. parts ofpotassiumiodide, 104 parts of pyridine and 400 parts by volume of dimethylformamide'is treated at 60 C. with 304 parts ofB-me'thoxyethyl-p-tolue ene-sulphonatedjadded in portions. After 17hours 'reac tion at C. .the mixture 'is poured onto parts of calcined'sodiumcarbonate and 1000 parts of ice water. The product is taken up inether, the solution is dried, filtered and evaporated. The residue isdistilled in a high vacuum. Boiling point C./0.02 mm. Hg.

4-[Bis(3-methoxyethyl)amino]-3-methyl-phenyl- N-methyl-carbamate 36parts of 4 [bis(fi-methoxyethyl) amino]-3-methylphenol and 0.2 part oftriethylenediamine are dissolved in 200 parts by volume of carbontetrachloride and treated dropwise with 10 parts of methylisocyanate.The solution is stirred for 14 hours at 40 C. and then evaporated. 4-[Bis(,3-methoxyethyl)amino] 3 methyl-phenyl-N-methylcarbamate isobtained as the residue [Compound No. 10].

aqueous solution EXAMPLE 8 3,5-Dimethyl-4(B-cyanethyl-methylamino)phenol 3 5-Dimethyl-4fi-cyanethyl-methylamino phenyl- N-methylcarbamate 47 parts of3,5-dimethyl-4(ficyanethyl-methylamino) phenol are dissolved in parts byvolume of ethyl acetate and treated with 0.4 part of triethylenediamineand, at 40 C., with 18 parts of methylisocyanate added in portions. Thesolution is kept for 14 hours at 40 C. and is evaporated. The residuecrystallises after some time. It is triturated with hexane and filtered01f. Melting point 63-67 C. [Compound No. 26].

EXAMPLE 9 A dusting agent manufactured using talc as the base andcontaining active susbtance No. 47 is applied to filter paper inconcentrations of 200, 100, 50, 25, 12 and 6 mg. of active substance perm. Groups of 5 test animals of the type indicated below are placed onthe treated substrates. After 24 hours the experiment is evaluated, thefollowing limiting concentrations for 100% mortality being ascertained:

Mg/m.

'Phyllodrbmid'ger'manica 12 Pe'r'iplaneta americaniz" 2SBlatta'orientalis 100 Tenebriom'olitor (imago) 100 'Dermestes frishchii(imago) 100 'Acheta domesticus Q. .50

-EXAMPLE 10- Potted young mallow plants (Malva sylvestrisj having sionsof the active substances No. 1, 3, 8, 9, 16, 19, 24,

-38, 47 and 57 containing 800 p.p.m. of active substance and are thenallowedto dry. The plants are infested with groups of 5 larvae of Orgyiagonostigma inthe L-3 stage.

19 After days'the experiment is evaluated, with 100% mortality of thetest animalsbeing established-for, each of the active substances.

a EXAMPLE Groups of 5 L-2 larvae of Proden ia litu rtz are placed,together with a leaf of Malva sylvestris"treated as'in 'Example l0,into'a covered Petri dish in which the moisture in the air is maintainedwith a moistened cottonwool pad.

In this dilution test leaves which were dipped in'solutions of 800, 400,200 and 100 p.p.m. are used. For active substance No. 1, the mortalityafter 2 days was EXAMPLE 12 The aphicidal action of the activesubstances No. 8, 24, 47 and 64 was determined for Aphis fabae (S) usingVicia faba as the test plant. Aqueous emulsions of the active substanceswere used in a concentration series of 800-100 p.p.m.

For the contact test, the solution was sprayed onto the infested plantfrom all sides by means of a chromatography atomiser. The evaluation wascarried out after 2 days by counting the dead animals with a handmagnifying glass.

Each of the 4 preparations achieved complete mortality at concentrationsof 800, 400, 200 and 100 p.p.m.

EXAMPLE 13 After 24 hours, percent After 48 hours, percent Compoundnumber. 1 8 2O 24 1 8 20 24 Concentration, p.p.m.:

l Not tested.

EXAMPLE 14 Action against Acarina (A) Rhipigephalus bursa.5 adult,hungry ticks are counted out into a test tube and dipped for l-2 minutesinto 2 ml. of an aqueous emulsion from a dilution series with 100, 50,and 1 p.p.m. of test substance. The test tube is then closed with astandardised cottonwool pad and inverted so that the active substanceemulsion is taken up by the cottonwool. The evaluation takes place after2 weeks.

Two repeats are run for each experiment.

Compound No. 57 achieved 100% mortality at 10 p.p.m.

Compound No. 59 achieved 100% mortality at 50 p.p.m.

(B) Boophilus microplus (larvae).--A test series and two repeats in eachcase using about 10-20 larvae were carried out with a similar dilutionseries. 100% mor- '20 tality was found at the following limitingconcentrations after 2 weeks:

Compound No.: p.p.m. I 10 -ls 38. -1o

(C) Drmanysszis gallinaQ- The test is carried out analogously to Metho'd(A)-'with about 10-20 mites. The evaluation takes place after 72 hours.

mortality was achieved at the following limiting concentrations:

Compound No.: p.p.m. 1 i': f. a 1 38 10 53 50 57 '10 What is claimedis: 1. A compound of the formula on, f t N-.-co-t R3 i wherein R",represents C -C alkyl and R", represents C C -alkyl substituted by anitrile group.

3. 2-(/S-cyanethyl-methyl-amino)-phenyl N methylcarbamate, as claimed inclaim 2.

4. 2-(cyanmethyl-ethyl-amino)-phenyl N methylcarbamate as claimed inclaim 2.

5. 2-(p-cyanethyl-ethyl-amino)'-phenyl N-'- methylcarbamate as claimedinclaim 2.

6. A compound according to claim 1 having the formula in which Rrepresents C -;-C -allrylorhas'the same 'meaningas R R representsC -Calkyl; substituted by a nitrile group and R' and R' which may be thesame'or different, each represents hydrogen, .methyl, ethyl orisopropyl. p c

7. 4-[bis(B-cyanethyDamino} =3 methylphenyl-N- methylcarbamate, as-claimed.in'clairn 6r g 8. 4-[bis(fl-cyanethyl)amino] '1 3;5-.dimethylphenyl- N-methylcarbamate, as claimed in claim. 6.1

21 9. A compound according to claim 1 having the formula CHg-NH-C O O inwhich R represents C -C -a1kyl or has the same meaning as R g, 'Rrepresents C C -a1ky1 substituted by a nitrile group and R2,, representshydrogen, methyl, ethyl or isopropyl.

10. 3- [bis(p-cyanethyl)-amino] 4 methyl-phenyl-N- methylcarbamate asclaimed in claim 9.

22 References Cited UNITED STATES PATENTS LEWIS GOTTS, Primary ExaminerD. H. TORRENCE, Assistant Examiner is 01. X.R.

